Dyes of the anthraquinone series



Patented Feb, 21, 1933 Ul llE ARNOLD SHEPHEBDSGN AND WELLIABI 'W'E LONDON, ENGLAND ED-H1511]: TATUIi I, OF BLACKLEY, MANCHES- TER, ENGLAND, ASSIGNOBS T0 IIVIPEE IAIL CHEMECAL INDUSTRIES LIMITED, OF

EYES OF THE ANTHRAQUINONESERIES No Drawing. Original application filed April 13, 1929, Serial No. 354,978, and in Great Britain April 19, 1928. Divided and this application filed October 10, 1929. Serial No. 398,808.

This invention relates to the production of new sulphonated anthraquinone derivatives; and it comprises a process wherein certain anthraquinone derivatives are treated with a suitable sulphonating agent, for instance soluble alkali sulphites, thereby converting them into the corresponding sulphonated anthraquinone derivatives; and it further comprises the new sulphonated anthraquinone thus produced; all as more fully hereinafter set forth and as claimed.

Our new sulphonated anthraquinone de rivatives may e represented by the probable general formula wherein R represents hydrogen or an alkyl Q group, fi represents hydrogen, a halogen or sulphonic group and R I'QPIGSQl'lL-S a residue having the probable formula wherein X represents hydrogen or a sulphonic group, and which contain only one such residue and at least one sulp-honic group. lVe have found that such new sulphonated anthraquinone derivatives may be advantageously used as dyes for various materials. These new compounds dye wool, silk and immunized cotton in level fast shades in an advantageous manner. These dyes give level fast bluislngreen to green shades on wool.

In our copending application Ser. No.

354,978 of which the presentapplication is a division, we describe the manufacture of new anthraquinone derivatives. These new anthraquinone derivatives may be represented by the probable general formula wherein R represents hydrogen or an alkyl group, R represents hydrogen, a halogen or a sulphonic group and R represents a residue having the following formula I H -X wherein X represents hydrogen or a sulphonic group and Y represents hydrogen or an acyl group, with anthraquinone deriva tives having the probable formula wherein R represents hydrogen or an alkyl group, R represents hydrogen, a halogen or a sulphonic group and R represents hydrogen or a halogen and 1n whlch only one R is a halogen. As stated in our aboveidentified copendin application, we have found that the condensation of an alphahalogenated anthraquinone with para-phenylenediamine proceeds much more smoothly in an aqueous medium than in an organic solvent tree from water. This is surprising as in the usual processes using simple aryl' amines instead of phenylenediamine, the condensation is effected in an organic solvent which must be free from traces of water. The products referred to above and obtained by our new.

method are pure and the yield is improved; an economy of materials being effected.

In the process of our above identified application, when it is desirable to produce sulphonated condensation products it is necessary to use compounds which initially contain a sulphonic group.

The present invention relates to a difi'erent and modified process of producing sulphonated anthraquinone derivatives of the type disclosed in our above identified application. In our present process we first effect a condensation in a manner similar to that or" our prior process and then subsequently treat thecondensation product thus formed with a suitable sulphonating agent to introduce the desired sulphonic groups. Our present process comprises condensing a phenylenediamine compound having the probable formula wherein X represents hydrogen or a sulphonic group, with an anthraquinone compound havmg the probable formula wherein R represents hydrogen or an alkyl group, R represents hydrogen, a halogen or asulphonic group and R represents a hydrogen or a halogen and in which only one It. represents a halogen and then treating the condensation product thus obtained with a sulphonating agent. The sulphonating agent may be 20 per cent oleum and the sulphonation may be efiected in the manner indicated in Example 2, again with condensation products which contain a halogen in the 2 position on the anthraquinone nucleus, the condensation product may be treated with a soluble alkali metal sulphite, thereby introducing a nuclear sulphonic group. For instance sodium sulphite may be usec. In our present process we may use unsulphonated anthraquinone condensation products or anthraquinone conot suitable strength such as per cent.

densation products which contain only one sulphonic group. Our present process produces a sulphonated or further sulphonated anthraquinone derivative of the above indicated type. Our method using a halogenated condensation product and treating the same with a soluble alkali metal sulphite is particularly advantageous. These halogenated anthraquinone derivatives have the probable formula wherein R represents hydrogen or a methyl group, X represents hydrogen or a sulphonic group and R represents a halogen. The treatment with the soluble alkali metal sulphite replaces the halogen with a sulphonic group.

Our application Ser. No. 354,978 is specifically directed to anthraquinone derivatives in whichthe R is hydrogen or halogen. The present application is specifically directed to the anthraquinone derivatives wherein R in the final products, is a sulphonic group. It is further directed to a process wherein sulphonic groups are introduced into the anthraquinone compounds by a subsequent sulphonating treatment.

The following typical examples illustrate our invention and serve to guide those skilled in the art in using our broad invention to the best advantage. In the examples the parts are by weight.

Example 1 Preparation of l-aminol-(p-amino-anilino) anthraqu1none-2-sulphon1c ac1d.

O NH2 10 parts of 2 d-dibromo-Lamino anthraquinone together with 5 parts of p-phenylene diamine and half a part of copper acetate are fed into 90 parts of 15 per cent caustic soda solution and boiled (at about 106 C.) for 2 hours. The precipitated base after filtering and washing with dilute acid may be purified by extraction with sulphuric acid It is thereby obtained in the form of a blue powder insoluble in water or alkalies but giving a red solution with hydrochloric acid.

The remaining bro-mine atom is now replaced by the sulphonic acid group, for example, by heating with sodium sulphite at l65 C. in aqueous phenol solution. The resultant sulphonic acid dissolves with a blue colour in water or alkalies the solution becoming red when strongly acidified. r The solution in methylated spirits is blue and in sulphuric acid blue changing to. green on addition of formaldehyde. From an acidulated bath, the new sulphonic acid dyes wool in level bluish-green shades of excellent fastness. It has the probable formula SOaH Ewample 2 Preparation of sulphonated 1 methyl amino i (p amino-anilino) anthraquinone.

A mixture of parts of 4-bro1no-1-methyh amino anthraquinone, 6 parts of p-phenylenediamine and part of copper acetate are introduced into 90 parts of hot saturated potassium carbonate solution (about 63 per cent). The whole is heated at130 C. for 3 hours, then diluted with water. The new dyestuif formed is insoluble and is filtered off and washed with dilute hydrochloric acid. -When crystallized from aniline it forms green crystals insoluble in water or dilute caustic soda solution but giving a red solution in concentrated hydrochloric acid. Its solution in sulphuric acid is purple changing to a bluish-green on addition of -formaldehyde. The solutions in acetic acid or methylated spirits are greenish-blue. new dyestuff showsgood affinity for acetate silk which is dyed in bluish-green shades of excellent fastness. On treatment with per cent oleum at C. it is converted into a soluble sulphonic acid which dyes wool in bluish-green shades.

hat we claim and desire to secure by Letters Patent is 1.. In the manufacture of new anthraquinone dyestuffs from paraphenylenediamine compounds, the process which comprises con- (lensing paraphenylenediamine with a halo- The Y genated anthraquinone compound having the probable formula O I l-R1 H l wherein R represents hydrogen or an alkyl group, R represents hydrogen, a halogen or a sulphonic group and R represents a hydro gen or a halogen and in which only one R represents a halogen said condensation b3? ing effected in an alkaline aqueous medium and then treating the condensation product thus obtained with a sulphonating agent.

2. In the manufacture of new anthraquinone dyestuffs the process which comprises condensing paraphenylenediamine with a halogenated anthraquinone compound having the probable formula v I ll R o R wherein R represents hydrogen or alkyl group, R represents hydrogen, halogen or a sulphonic group and R represents hydrogen or a residue having the probable for- 1 mula wherein X represents hydrogen or asulphonic group, and which contains only one such residue and at least one 'sulphonic group and in which when 3; and R represent hydrogen and said residue respectively, R represents an alkyl group, the said anthraquinone compounds being blue to green powders soluble in water and alkalies giving a solution having a blue colour which upon being strongly acidified becomes red, and being soluble in methylated spiritsgiving a blue solution and being soluble in sulphuric acid giving a blue solution which on addition of formaldehyde changes to green, the said anthraquinone compounds dyeing wool in level fast bluish green shades.

5. As new products, sulphonated anthraquinone compounds suitable as dyestuffs and having the probable formula wherein R represents hydrogen or an alkyl group, and X represents hydrogen or a sul phonic group and in which when X represents a sulphonic group R represents an alkyl group, the said anthraquinone compounds being blue to green powders soluble in water and alkalies giving a solution hav ing a blue colour which upon being strongly acidified becomes red, and being soluble in methylated spirits 'iving a blue solution and being soluble in sulphuric acid giving a blue solution which on addition of formaldehyde changes to green, the said 'anthraquinone compounds dyeing wool in level fast bluish green shades.

6. As a new product, the sulphonated anthraquinone compound suitable as a dyesuu and having the probable formula lTIHa 7. In the manufacture of new anthraquinone dyestuffs, the process which comprises condensing a phenylenediainine compound having the probable forn'iula with a halogenated anthraquinone compound having theprobable formula I with halogenated anthraquinone compound having the probable formula N 1 cell st iierein n 'esents a haloi only one R s a I sation being effected in the presence of an aqueous solution of an alkaline carbonate andthen treating the condensation product thus obtained with oleum.

9. tl e manufacture of new anthraquinone dyestuffs, tne process which comprises condensing a phenylenediamine compound having the probable formula with halogenated anthraquinone compound having the probable formula an alkaline aqueous medium and then treating the condensation product thus obtained with oleum.

10. As a new product, a sulphonated anthraquinone compound suitable as dyestui f and having the probable formula SOsH the said dyestuff dyeing wool in bluish-green shades.

11. As new products, sulphonated anthraquinone compounds suitable as dyestuffs and having the probable formula mixture thus obtained to about 106 C. until reaction and condensation have been effected, isolating and recovering the condensation product thus obtained, mixing the said condensation product with sodium sulphite in an aqueous phenol solution, heating the mixture to about 165 C. until a soluble sulphonic acid is obtained and recovering said sulphonic acid.

18. In the manufacture of new anthraquinone dyestufis, the process which comprises mixing together about 10 parts of 4- bromo-l-methylaminoanthraquinone, about 6 parts of para-phenylenediamine, a small amount of copper acetate and a hot saturated potassium carbonate solution, heating the aqueous mixture thus obtained to about 130 C. until reaction and condensation are effected, isolating and recovering the condensation product thus obtained, mixing the said condensation product with 20 per cent oleum,

soluble sulphonic acid is obtained and then isolating said sulphonic acid. 1

14. In the manufacture of new anthraquinone dyestuffs, the process which comprises mixing together a halogenated anthraquinone compound having an amino groupingin the l-position and a halogen substituent in the 4-position with approximately an equimolecular proportion of para-phenylenediamine and a small amount of copper acetate in an alkaline aqueous medium, heating the aqueous mixture thus obtained until reaction and condensation are effected, isolating and recovering the condensation product thus obtainedand then reacting said condensation product with a sulphonated agent to convert said condensation product into a soluble sulphonic acid derivative.

In Witness whereof we aflix our signatures. ARNOLD SHEPHERDSON. WVILLIAM VVYNDHAM TATUM.

heating the mixture to about 40 C. until a 

